JP3082479B2 - Negative radiation-sensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative-type radiation-sensitive resin composition useful as a resist for producing highly integrated circuits responsive to various radiations.

[0002]

2. Description of the Related Art In the field of fine processing represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration, in recent years, a lithography process capable of performing fine processing of 0.5 μm or less with good reproducibility. It has been recently discovered that applying a resist to a phase shift lithography process improves the radiation contrast and thus achieves higher resolution. However, when a positive resist is applied to the phase shift lithography process, when forming an isolated pattern, the intensity of radiation is attenuated due to a phase shift in a boundary region of a shifter used for phase shift.
There is a problem that a portion which must be removed by development remains. Against this background, a chemically amplified negative compound containing a compound that generates an acid upon irradiation with radiation (hereinafter, referred to as an “acid generator”) and becomes insoluble in a developer by a crosslinking reaction with the acid. Type resist (for example, alkali-soluble resin such as novolak resin,
A resist composed of an acid generator such as a quinonediazide compound and a cross-linking agent such as methylolmelamine) has attracted attention as a negative resist for a phase shift lithography process. However, the conventional chemically amplified negative resist has a problem in that the generated acid remains inside the resist pattern, so that the acid causes a problem such as corrosion of integrated circuit device manufacturing equipment and a substrate, and particularly, a problem with the substrate. There is a problem that the adhesiveness with the resist pattern is reduced, and the formed resist pattern is easily peeled off from the substrate. Further, as a general problem not only in the negative type but also in the chemically amplified resist, from irradiation of radiation (hereinafter referred to as "exposure") to heating after exposure (hereinafter referred to as "post-exposure baking") or development. Takes longer, the sensitivity, resolution, resist pattern shape, etc. change.
ED) "phenomenon is recognized, and it is desired to improve the phenomenon and to establish a technique capable of forming a good resist pattern with good reproducibility.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an improved novel negative-working radiation-sensitive resin composition. Another object of the present invention is to provide a negative radiation-sensitive resin composition suitable as a negative resist having excellent adhesion to a substrate. Still another object of the present invention is to provide
An object of the present invention is to provide a negative-type radiation-sensitive resin composition which always shows stable resist performance and does not show a PED phenomenon regardless of the length of time from exposure to post-exposure baking or development.

[0004]

According to the present invention, the above object is represented by the following structural formula (1) having (a) an alkali-soluble resin and (b) a substituent capable of being released by irradiation with radiation. This is achieved by a negative-type radiation-sensitive resin composition containing an aromatic crosslinking agent.

Wherein L represents a substituent which can be released by irradiation of radiation, Ar represents an n-valent aromatic hydrocarbon group, and R ¹
Represents a hydrogen atom, an alkyl group having 4 or less carbon atoms, an alkoxyalkyl group having 6 or less carbon atoms or a trialkylsilyl group having 6 or less carbon atoms, and R ² and R ³ are each independently a hydrogen atom or a carbon atom R ⁴ represents a hydrogen atom, a halogen atom, an alkyl group having 4 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, an aryl group having 10 or less carbon atoms, or an aralkyl group having 10 or less carbon atoms. , N,
x, y and z are n = x + y + z, x ≧ 1, y ≧ 1,
It is an integer satisfying the relationship z ≧ 0. Where x ≧ 2, y ≧
When 2 or z ≧ 2, a plurality of R ¹ ,
R ² , R ³ or R ⁴ may be the same or different. Hereinafter, the present invention will be described in detail, which will clarify the objects, configurations and effects of the present invention.

The most important feature in the aromatic crosslinking agent present invention, without using a so-called acid generator lies in the use of specific aromatic crosslinking agent having a substituent capable of leaving upon exposure. That is, the aromatic crosslinking agent represented by the structural formula (1) in the present invention (hereinafter referred to as “crosslinking agent (A)”) is thermally stable due to the presence of the substituent L. In accordance with the mechanism shown in the following model reaction, the substituent L is released by exposure and becomes thermally unstable, and then a post-exposure bake causes a crosslinking reaction with the alkali-soluble resin.

Embedded image (Here, L, Ar and R ¹ are the same as in the structural formula (1).)

In the structural formula (1), the substituent L is a substituent capable of being released by exposure to form, for example, a phenolic hydroxyl group in the crosslinking agent (A).
Examples include acyl groups, nitro-substituted aralkyl groups, acyl-substituted aralkyl groups, formyl-substituted aralkyl groups, and Schiff bases of formyl-substituted aralkyl groups.

As such a substituent L, a nitro-substituted aralkyl group represented by the following structural formulas (2) to (4) is preferable.

Embedded image (Here, R ⁵ represents an alkyl group having 1 to 3 carbon atoms, R ⁶ and R ⁷ each independently represent a hydrogen atom or a nitro group, and at least one of R ⁶ and R ⁷ is A nitro group, and R ^{8 to} R ¹⁰ independently represent a hydrogen atom, a nitro group or an alkyl group having 1 to 4 carbon atoms.)

[0008]

Embedded image (Where R ¹¹ represents an alkyl group having 1 to 3 carbon atoms;
¹² represents a hydrogen atom, a nitro group or an alkyl group having 1 to 4 carbon atoms. )

[0009]

Embedded image (Where R ¹³ represents an alkyl group having 1 to 3 carbon atoms;
¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a nitro group, but at least one of R ¹⁴ and R ¹⁵ is a nitro group, and R ¹⁶ is a hydrogen atom, a nitro group or a C 1 to C 4 Represents an alkyl group. )

In the structural formula (1), Ar is preferably a group represented by the following structural formulas (5) to (10).

Embedded image

[0011]

Embedded image

[0012]

Embedded image (Wherein, X represents a single bond, -S-, -SO ₂ -, -CO- or -C (R
¹⁷ ) (R ¹⁸ )-, wherein R ¹⁷ and R ¹⁸ are each independently
It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )

[0013]

Embedded image (Here, R ^{19 to} R ²² independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

[0014]

Embedded image (Here, R ²³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

[0015]

Embedded image (Here, R ^{24 to} R ²⁶ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

In the structural formula (1), R ¹ represents a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a methoxymethyl group, a 1-methoxyethyl group,
An ethoxyethyl group, a 1-propoxyethyl group, a 1-butoxyethyl group, a tetrahydropyranyl group, a trimethylsilyl group and the like are preferable. More preferred R ¹ is a hydrogen atom,
Examples include a methyl group, an ethyl group, a t-butyl group, and a tetrahydropyranyl group.

In the structural formula (1), R ² and R ³ represent a hydrogen atom, a methyl group, an ethyl group, an isopropyl group,
A t-butyl group and the like are preferred.

In the structural formula (1), R ⁴ represents a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group,
A propoxy group and a butoxy group are preferred.

These crosslinking agents (A) can be used alone or
A mixture of more than one species can be used. Crosslinking agent (A)
Is used per 100 parts by weight of the alkali-soluble resin,
Usually, it is 5 to 100 parts by weight, preferably 10 to 75 parts by weight, more preferably 15 to 50 parts by weight. If the amount of the cross-linking agent (A) is less than 5 parts by weight, the cross-linking reaction cannot proceed sufficiently, which may lead to deterioration of the resist pattern shape at the time of development, film reduction, and the like. If the amount exceeds the above range, the applicability and the like when used as a resist solution tend to decrease.

Alkali-Soluble Resin Next, the alkali-soluble resin (hereinafter referred to as "resin (B)") in the present invention has a property of being soluble in an alkali developing solution. Resins, poly (hydroxystyrene) -based resins, and the like.

The novolak resin is obtained by polycondensing phenols with aldehydes and / or ketones in the presence of an acidic catalyst. Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-cresol
-Butylphenol, 2,3-xylenol, 2,4-
Xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p
-Phenylphenol, hydroquinone, catechol,
Examples thereof include resorcinol, 2-methylresorcinol, pyrogallol, 1-naphthol, 2-naphthol, bisphenol A, dihydroxybenzoic acid ester, and gallic acid ester. These phenols are used alone or in combination of two or more.

The aldehydes include, for example, formaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde,
α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-
Hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde,
Examples include p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural and the like.
Of these, formaldehyde is particularly preferred.

When formaldehyde is used as the aldehyde, as a formaldehyde generating source, for example, in addition to formalin, trioxane, paraformaldehyde, etc., hemiformal such as methylhemiformal, ethylhemiformal, propylhemiformal, butylhemiformal, phenylhemiformal, etc. And the like.
Of these, formalin and butyl hemiformal are particularly preferred.

The ketones include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Among them, acetone is particularly preferred.

These aldehydes and / or ketones are used alone or in combination of two or more.
The amount of the aldehydes and / or ketones to be used is preferably 0.7 to 3 mol per 1 mol of the phenol,
More preferably, it is 0.75 to 1.3 mol.

The phenols and aldehydes and / or
Or acidic catalysts used for polycondensation with ketones, for example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid,
Paratoluenesulfonic acid and the like can be mentioned. The use amount of these acidic catalysts is usually 1 × 10 ^{-4 to} 5 × 10 ^-1 mol per 1 mol of phenols.

In the polycondensation of phenols with aldehydes and / or ketones, water is usually used as a reaction medium, but the phenols used are not dissolved in an aqueous solution of aldehydes and / or ketones. If the reaction becomes non-uniform from the beginning of the reaction, a hydrophilic solvent can be used as the reaction medium. Such hydrophilic solvents include, for example, methanol, ethanol, propanol,
Alcohols such as butanol, diethylene glycol dimethyl ether, 1,2-dimethoxyethane, 1,2-
Examples include ethers such as diethoxyethane and cyclic ethers such as tetrahydrofuran and dioxane.
The amount of the reaction medium used is usually 20 to 1,000 parts by weight per 100 parts by weight of the reaction raw material.

Examples of the method of polycondensation of phenols with aldehydes and / or ketones include a method in which reaction components such as phenols, aldehydes and / or ketones, and an acidic catalyst are collectively charged and polycondensed. A method of polycondensation while gradually adding phenols, aldehydes and / or ketones and the like in the presence of a catalyst during the reaction can be adopted. The temperature of the polycondensation of phenols with aldehydes and / or ketones is usually
It is about 10 to 200 ° C. After completion of the polycondensation reaction, the temperature of the reaction system is raised to, for example, 100 to 230 ° C., and volatile components are removed under reduced pressure to recover the generated novolak resin.

The polystyrene-equivalent weight average molecular weight (hereinafter, referred to as “Mw”) of the novolak resin used in the present invention is usually 2,000 to 25,000, preferably 3,500 to 15,000. If the Mw of the novolak resin is less than 2,000, developability, heat resistance and the like tend to decrease, and if it exceeds 25,000, developability, sensitivity, resolution and the like may be insufficient.

The poly (hydroxystyrene) -based resin has a repeating unit (hereinafter, referred to as “repeating unit (a)”) corresponding to a structure in which a polymerizable double bond portion of hydroxystyrene is cleaved. It is united. Examples of the hydroxystyrenes include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 3-chloro-4-hydroxystyrene, 4-chloro-3-hydroxystyrene, 4-bromo-3-hydroxystyrene, 3-ethyl-4-hydroxystyrene, 3
-Propyl-4-hydroxystyrene, 3-t-butyl-4-hydroxystyrene, 3-phenyl-4-hydroxystyrene, 3-naphthyl-4-hydroxystyrene, 3-benzyl-4-hydroxystyrene, styryl-4- Hydroxystyrene, 3-vinyl-4-hydroxystyrene, 3-propenyl-4-hydroxystyrene, 3-cumyl-4-hydroxystyrene, 2-methyl-4-hydroxystyrene, 2,6-dimethyl-4-hydroxystyrene and the like Is mentioned.

The poly (hydroxystyrene) resin includes, in addition to the repeating unit (a), for example, methyl (meth) acrylate, ethyl (meth) acrylate, glycidyl (meth) acrylate, propyl (meth) acrylate, Methyl vinyl ether, t-butyl vinyl ether, styrene, α
-Methylstyrene, p-methylstyrene, chlorostyrene, maleic anhydride, vinyl acetate, vinylpyridine, vinylpyrrolidone, (meth) acrylonitrile, (meth)
Acrylamide, methyl vinyl ketone, ethyl vinyl ketone, vinyl dimethylamine, vinyl diethylamine,
Repeatable units in which the polymerizable double bond such as methyl vinyl thioether and ethyl vinyl thioether have been cleaved (hereinafter referred to as
It is referred to as “repeating unit (b)”. ) May be included.
The proportion of the repeating unit (b) in all the repeating units is usually 20% or less, preferably 10% or less.

The Mw of the poly (hydroxystyrene) resin used in the present invention is usually from 5,000 to 30.
0000, preferably 10,000 to 150,000
It is. Mw of the poly (hydroxystyrene) resin is
If it is less than 5,000, the heat resistance tends to decrease and 3
If it exceeds 000, the developability, resolution, coatability and the like may be insufficient.

The resin (B) may be used by hydrogenating the remaining unsaturated bonds. In this case, the hydrogenation rate is usually 70% or less, preferably 50% or less, and more preferably 40% or less. When the hydrogenation rate of the resin (B) exceeds 70%, the solubility in an alkaline aqueous solution used as a developer described later decreases, the ability to form a resist pattern becomes insufficient, and the dry etching resistance also decreases. , Etching failure may occur.

In the present invention, the novolak resin,
The resin (B) such as the poly (hydroxystyrene) -based resin or a hydrogenated product thereof can be used alone or in combination of two or more.

Additives Various additives such as a dissolution inhibitor, a dissolution promoter, a sensitizer, and a surfactant can be added to the composition of the present invention, if necessary.

The dissolution inhibitor is used when the alkali solubility of the resin (B) is too high. The dissolution inhibitor reduces the alkali solubility of the resin (B) to improve the resist pattern forming ability. The larger the compound, the more effective.

The dissolution inhibitor is not particularly limited as long as it has the above-mentioned action. Preferred examples thereof include sulfone compounds such as diphenylsulfone and dinaphthylsulfone, phenyl p-toluenesulfonate, -Naphthalenesulfonic acid phenyl ester, 2
And sulfonic acid ester compounds such as naphthalenesulfonic acid phenyl ester. The mixing amount of these dissolution inhibitors is usually 50 parts per 100 parts by weight of the resin (B).
It is at most 30 parts by weight, preferably at most 30 parts by weight.

The dissolution promoter is used when the alkali solubility of the resin (B) is too low, contrary to the dissolution inhibitor, and enhances the alkali solubility of the resin (B) to improve the resist pattern forming ability. This shows the effect of improving
The dissolution promoter is not particularly limited as long as it has such an effect, and examples thereof include a low-molecular phenol compound. Preferred low molecular weight phenol compounds are compounds having about 2 to 6 benzene rings. The amount of the dissolution promoter to be added is generally 50 parts by weight or less, preferably 30 parts by weight or less, per 100 parts by weight of the resin (B).

These dissolution inhibitors and dissolution promoters are
By adjusting the alkali solubility of the composition, it shows an effect of improving or optimizing the pattern forming ability as a resist, and by itself, heating before exposure (hereinafter, referred to as heating before exposure).
It is called "preliminary firing". ), In the process of forming a resist pattern such as exposure, post-exposure baking, and development, a compound that hardly changes chemically is used.

The sensitizer absorbs radiation energy and transmits the energy to the crosslinking agent (A), thereby improving the sensitivity of the composition of the present invention. The sensitizer is not particularly limited as long as it has the above-mentioned action, and preferred examples thereof include acetone, benzene, acetophenones, benzophenones,
Examples include naphthalenes, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines and the like. The amount of the sensitizer to be added is generally 50 parts by weight or less, preferably 30 parts by weight or less, per 100 parts by weight of the resin (B).

Further, the above-mentioned surfactant has an effect of improving the coating property and the developing property of the composition of the present invention. The surfactant is not particularly limited as long as it has the above-mentioned action. Examples thereof include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, and polyoxyethylene octyl phenyl ether. Nonionic surfactants such as ethylene nonyl phenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate; KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), an organosiloxane polymer; and (meth) acrylic acid (co) polymer. Certain polyflow Nos.
75, no. 95 (trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo), F-top EF301, EF303, EF352
(Trade name, manufactured by Shin-Akita Kasei), MegaFac F171, F
172, F173 (trade name, manufactured by Dainippon Ink), Florado FC430, FC431 (trade name, manufactured by Sumitomo 3M), Asahigard AG710, Surflon S-38
2, SC-101, SC-102, SC-103, SC
-104, SC-105, SC-106 (trade name, manufactured by Asahi Glass) and the like. The amount of these surfactants is usually 2 parts by weight or less per 100 parts by weight of the solid content of the composition.

In the composition of the present invention, the incorporation of a dye or a pigment makes it possible to visualize the latent image in the exposed area, thereby reducing the effects of halation at the time of exposure. In addition, other additives such as a storage stabilizer, an antifoaming agent, and an adhesion aid can be appropriately compounded.

Preparation of Composition Solution The composition of the present invention contains the above-mentioned resin (B) and cross-linking agent (A), and various additives optionally added. Is, for example, dissolved in a solvent so that the solid content concentration is 20 to 40% by weight,
For example, a composition solution is prepared by filtering with a filter having a pore size of about 0.2 μm. Accordingly, the composition of the present invention comprises, in one aspect, a polymer (B)
And a crosslinking agent (A), and, if necessary, various additives, and in other embodiments, a solution in which the above components are dissolved in a solvent. Will.

Examples of the solvent used for preparing the composition solution include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl. Ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, 4- Heptanone, 2-hydroxy Methyl propionate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropionic acid ethyl, ethyl ethoxy acetate, hydroxyethyl acetate, 2-hydroxy-3-methyl-butyric acid methyl, 3
Examples thereof include methyl-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, and ethyl pyruvate. These solvents are used alone or in combination of two or more.

The solvent may further include N-
Methylformamide, N, N-dimethylformamide,
N-methylformanilide, N-methylacetamide,
N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether,
Dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-
Nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate,
γ-butyrolactone, ethylene carbonate, propylene carbonate,
A high boiling solvent such as ethylene glycol monophenyl ether acetate can also be added.

Next, formation of a resist pattern will be described. When forming a resist pattern from the composition of the present invention, the composition solution, by means of spin coating, casting coating, roll coating, etc., for example, silicon wafers, on a substrate such as a wafer coated with aluminum By coating, a resist film is formed. Next, after pre-baking is preferably performed, exposure is performed through a predetermined mask pattern, post-exposure baking is performed at a temperature at which a crosslinking reaction occurs, and then development is performed with a developer.

When a resist pattern is formed using the composition of the present invention, post-exposure baking is an essential step. The crosslinking agent (A) in the composition of the present invention is thermally stable due to the presence of the substituent L. However, the substituent L is liberated by exposure to light, for example, a phenolic compound, and becomes thermally insoluble. It becomes stable, and by the subsequent post-exposure baking, the crosslinking reaction with the resin (B) proceeds only in the exposed portion,
By becoming insoluble in the developer, the effects of the present invention are exhibited. A typical mechanism of a crosslinking reaction at the time of forming a resist pattern in the present invention is exemplified below.

Embedded image

The post-exposure baking temperature is preferably 90
To 250 ° C, more preferably 100 to 220 ° C, particularly preferably 130 to 190 ° C. When the temperature of the post-exposure baking is lower than 90 ° C., the crosslinking agent (A) exists relatively stably even after the release of the substituent L, and the progress of the crosslinking reaction tends to be insufficient, making it difficult to form a good resist pattern. When the temperature is higher than 250 ° C., the crosslinking agent (A) in which the substituent L present in the unexposed portion is not released also participates in the crosslinking reaction, and the contrast between the exposed portion and the unexposed portion, There is a possibility that the shape and the like of the resist pattern may be reduced.

The radiation used for exposure is, for example, visible light, ultraviolet light, far ultraviolet light (eg, KrF excimer laser), X-ray (eg, synchrotron radiation), gamma ray, charged particle beam (eg, electron beam, proton beam, etc.). ,
It is appropriately selected from molecular beams and the like.

As the developer for the composition of the present invention,
For example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine , Tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-
Alkaline compounds such as [5,4,0] -7-undecene and 1,5-diazabicyclo- [4,3,0] -5-nonane are usually added in an amount of 1 to 10% by weight, preferably 2 to 5% by weight.
An alkaline aqueous solution dissolved so as to have a concentration of is used. Further, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant may be added to the developer. When development is performed using a developer composed of an alkaline aqueous solution as described above, generally, development is followed by washing with water.

[0051]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, it should be understood that these Examples illustrate preferred embodiments of the present invention.
The present invention is not limited at all by the examples. The measurement of Mw and the performance evaluation of the resist were performed by the following methods.

Mw: Tosoh Corporation GPC column (G2
000H _XL : 2 pcs, G3000H _XL : 1 pcs, G4000
H _XL : 1), using gel permeation chromatography using monodisperse polystyrene as a standard under the analysis conditions of a flow rate of 1.0 ml / min, an elution solvent of tetrahydrofuran, and a column temperature of 40 ° C.

General performance of resist: A resist pattern is formed on a resist film formed on a silicon wafer.
The shape, developability and the like were observed using an optical microscope and a scanning electron microscope.

Peeling test: The resist pattern formed on the substrate on which aluminum was deposited was subjected to peeling test.
The degree and the like were observed using an optical microscope.

PED test: A resist pattern formed by baking and developing immediately after exposure to a resist film formed on a silicon wafer and a resist pattern formed by baking and developing after exposure after being stored in the air for one week. Were compared in terms of line width, shape, and the like.

Synthesis Example 1 176 g (1.0 mol) of pt-butoxystyrene and 8.2 g (0.05 mol) of azobisisobutyronitrile were dissolved in 100 ml of dioxane, and the temperature of the reaction solution was 70 ° C. And reacted for 24 hours. After the reaction, unreacted monomers were removed by performing reprecipitation several times, and poly (p-
(t-butoxystyrene) was obtained. Then, this poly (p
-T-butoxystyrene) is hydrolyzed with an acid to give a poly (p-hydroxystyrene) resin (Mw = 30,00).
0) was obtained. This resin is referred to as a resin (B1).

Synthesis Example 2 108 g (1 mol) of p-cresol, 179 g of 37% by weight formalin (2.2 mol of formaldehyde) and 88 g of 50% by weight aqueous sodium hydroxide solution (1.1 mol of sodium hydroxide) were added to 10 parts of The reaction was carried out at a temperature of not more than ℃ for 5 days. Then, the reaction solution was neutralized with acetic acid so that the temperature did not exceed 15 ° C. After neutralization, the precipitate was separated by filtration, washed several times with a large amount of water, dried, and dried to give pale yellow 2,6.
-Dimethylol-p-cresol (hereinafter referred to as "DMP") was obtained. Subsequently, 16.8 g (0.1 mol) of DMP and 16.3 g (0.0 mol of o-nitrobenzyl chloride) were added.
95 mol), 4.2 g (1.05 mol) of sodium hydroxide and 100 ml of methanol were charged into a flask and reacted under reflux for 8 hours. After the reaction, the content was poured into 2 liters of water to precipitate a reaction product.
The precipitate was separated by filtration, washed several times with a large amount of water, and further washed several times with toluene. Then, it was dried to obtain o-nitrobenzyl ether of DMP represented by the following structural formula (11) (hereinafter, referred to as “DMP-N”).

Embedded image

Example 1 After dissolving 100 parts by weight of the resin (B1) and 25 parts by weight of DMP-N in 418 parts by weight of ethyl 2-hydroxypropionate, the solution was filtered through a membrane filter having a pore size of 0.2 μm to obtain a composition solution. Prepared. After applying this composition solution onto a silicon wafer using a spinner, 9
Preliminary baking was performed at 0 ° C. for 120 seconds to form a resist film having a thickness of 1.0 μm. A mask pattern is adhered to this resist film, and an exposure machine “MBK-
After exposing with KrF excimer laser using “400TL-N”, baking was performed at 170 ° C. for 300 seconds. Next, the resist film was developed by an immersion method at 23 ° C. for 1 minute using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, washed with ultrapure water for 30 seconds, and dried. As a result, a negative resist pattern having a good shape was formed at an exposure dose of 300 mJ / cm ² , and there was no undeveloped portion left undeveloped and the developability was good. In addition, a peeling test was performed on a resist pattern formed using the resist solution. No peeling phenomenon was observed for a fine resist pattern having a line width of 1 μm or less. Further, after exposing the resist film at the same exposure dose as above, a PED test was performed. As a result, there was almost no difference in the line width, shape, etc. between the resist pattern that was subjected to post-exposure baking and development immediately after exposure and the resist pattern that was subjected to post-exposure baking and development after storage for one week, and the PED phenomenon occurred. Was not found.

[0059]

The negative-type radiation-sensitive resin composition of the present invention can form a resist pattern having a good shape, is excellent in developability, and is particularly excellent in adhesiveness to a substrate and has excellent light exposure. Regardless of the length of time from baking to post-exposure baking or development, stable resist performance can always be exhibited. Therefore, the negative-type radiation-sensitive resin composition of the present invention is extremely useful as a resist for producing highly integrated circuits such as semiconductor devices.

Continuation of the front page (72) Inventor Akira Tsuji 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-2-248953 (JP, A) JP-A-2-150848 (JP, a) JP Akira 64-54441 (JP, a) JP flat 4-13725 (JP, a) JP flat 4-367864 (JP, a) (58 ) investigated the field (Int.Cl. ⁷ G03F 7/004 G03F 7/038 H01L 21/027

Claims (1)

(57) [Claims] (1) an alkali-soluble resin, and (b)
A negative-type radiation-sensitive resin composition comprising an aromatic cross-linking agent represented by the following structural formula (1) having a substituent capable of being released by irradiation with radiation. Embedded image (Wherein, L represents a substituent capable of being released by irradiation with radiation, Ar represents an n-valent aromatic hydrocarbon group, R ¹ represents a hydrogen atom, an alkyl group having 4 or less carbon atoms, and an alkyl group having 6 or less carbon atoms. Represents an alkoxyalkyl group or a trialkylsilyl group having 6 or less carbon atoms, R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 4 or less carbon atoms, R ⁴ represents a hydrogen atom,
A halogen atom, an alkyl group having 4 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, an aryl group having 10 or less carbon atoms or an aralkyl group having 10 or less carbon atoms, wherein n, x, y and z are n = x + y + z, It is an integer that satisfies the relation of x ≧ 1, y ≧ 1, and z ≧ 0. However, when x ≧ 2, y ≧ 2 or z ≧ 2, a plurality of R ¹ , R ² , R ³ or R ⁴ may be the same or different. )